A smectic B (S,) solvent may provide a very highly ordered, and possibly oriented, host medium for polymerization processes. Photochemical polymerizations of two bisacrylic monomers were therefore carried out in a SBmedium. The process conditions were chosen on the basis of a preliminary study of the monomer-solvent binary system carried out by differential scanning calorimetry (D.S.C.), optical microscopy and X-ray diffraction. The polymerization was then studied by D.S.C. at different reaction times. These measurements showed clearly that there is a point along the reaction path at which the growing polymer chains start segregating from the solvent and the mesomorphic bulk no longer acts as a reaction solvent but only as a reservoir for the ponomer. The polymer chains from that point keep growing only upon or between the faces of the SBlayers. Electron microscopy observations showed that the morphology of the final polymer is affected by this interlayer process.